In this paper, four novel silver(I) sulfonate coordination polymers containing neutral ligands, namely, [Ag2L1(biim)2] • 2H2O( 1), AgL2(biim) (2), [Ag(HL3)(Pic)2] • H2O( 3), and [Ag3(L3)(HL3)(4,4’-bipy)3(H2O)2] • 4H2O( 4), have been synthesized [L1 = 3-carboxy-4-hydroxybenzenesulfonate, L2 = p-aminobenzenesulfonate, H2L3 ) p-hydroxybenzenesulfonic acid, biim ) 1,1’-(1,4-butanediyl)-bis(imidazole),Pic =β-picoline,4,4‘-bipy = 4,4’-bipyridine].For compounds1 and 2, Ag(I) cationsare bridged by biim ligands to form a one-dimensional (1D) “zigzag” chain, and L1 and L2 sulfonate ligands are not coordinated to the silver cation. Compound 3 has a dimeric structure in which two silver cations are bridged by two HL3 ligands. For compound 4, L3 ligand coordinates to a silver cation as a monodentate ligand, and Ag(I) cations are bridged by 4,4’-bipy ligands to form a 1D chain. Compound 1 contains water dimers, while compound 4 contains water trimers. Compounds 1-3 display room-temperature photoluminescence.